Methods of killing insects and mites using certain phosphorus containing organotin compounds

ABSTRACT

A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula   wherein x can be oxygen or sulfur; R1 and R2 can be the same or different and can be selected from lower alkyl, lower alkoxy, cycloalkoxy, thiophenyl, haloalkyl, alkoxythioalkyl, thiocyano, furfuryloxy, alkyldioxolanealkoxy and sulfolaneyloxy.

United States Patent n91 Baker [451 Nov. 11, 1975 METHODS OF KILLING INSECTS AND MITES USING CERTAIN PI-IOSPIIORUS CONTAINING ORGANOTIN COMPOUNDS {75] Inventor: Don R. Baker, Orinda. Calif.

[73] Assignee: Staufier Chemical Company.

Westport, Conn.

22 Filed: June 24,1974

211 Appl. No.: 482,034

Related US. Application Data [60] Division of Ser. No. 293.974. 0m. 2. 1972. abandoned, which is a continuation-in-part of Set. No 208.046. Dec. 10. [97L abandoned.

FOREIGN PATENTS OR APPLICATIONS l.l63.738 9/]969 United Kingdom PIIHIIH) E.\'aminer-Albert T. Meyers Assistant Emml'nerLe0nard Schenkman Auorner, Agent. or Firm-Daniel C. Block [57] 2 ABSTRACT A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following ge neric formula wherein x can be oxygen or sulfur; R and R can be the same or different and can be selected from lower alkyl. lower alkoxy, cycloalkoxy. thiophenyl, huloalkyL alkoxythioalkyl. thiocyano. furfuryloxy. alkyldioxolanealkoxy and sulfolaneyloxy.

14 Claims. No Drawings term alky] is defined as branched or straight chain alkyls having from one to about six carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION CROSS-REFERENCE T RELA ED A P IC T 5 In the practice of the present invention, the com- This application is a division of application Ser. No. f of the pre sem f l are mafmfacwred b 293974, filed Oct 2. 972, which is a continuatiomim reacting an alkyl tin halide with an alkali phosphate in part of application No 208,046, filed 10, a neutral solvent. The halide moiety in the alkyl tin ha- 197] both now abandoned lides can be selected from a group consisting of chlorine, bromine and iodine. After the compounds of the BACKGROUND F HE INVEN I present invention are formed, they can be applied to Among the many insecticidal and miticidal the habitat in an effective amount to control respective pounds available, the organotin compounds have and F reached a relatively high degree of commercial success. The l examples Illustrate the mems of the Specifically, the organotins described in U.S. Pat. Nos. Present mvem'oni 3,264, I 77, and are USfid. 1 These compounds, however, suffer from considerable instability due to the presence of an ester linkage to the 5 tin atom. Thus, these compounds are quite susceptible H 1 to hydrolysis on use. Additionally, the organotin com- S" S P 2 pounds described in US. Pat. Nos. 3,321,361 and 3,321,365 are useful as insecticides. However, these 3 compounds are quite toxic to vegetation and thus have extremely limited use.

A mixture was formed contammg 10.1 grams of tricy- BR EF DESCRIPTION OF THE INVENTION clohexyltin chloride (0.025 M), 7.6 grams potassium I diisopropyl dithiophosphate (0.03 M) and 100 ml. of It has been dlsfovered certiflrf organot"? acetone. The mixture was heated to reflux for 1.5 hours Pounds have relatively low phytotoxlclty Propemes and and then filtered. The filtrate was evaporated in vacuo are relatively stable. These organotln compounds may and taken up in water (100 m1) and methylene ch1o be defined by the following generic formula ride (100 ml. dried over magnesium sulfate and evaporated in a vacuum to yield 6.5 grams of product. GIL-CH, 2 H EXAMPLE 2 CH,CH,

X cH, cH, s --Sn-SP \R /CHJ ere-cu, z -SnS-P 0CH,CH

CH; 2 cii,-cH 012 \CH cH, CH,

The procedure of Example I was repeated in its entirety except 8.4 grams of potassium diisobutyl dithiowherein x can be oxygen or Sulfur; RI d R2 can b phosphate was substituted for the potassium diisoprothe same or different and can be selected from a group PY dlthlophosphateconsisting of lower alkyl, lower alkoxy, cycloalkoxy, other compounds made In a slmllal manner thiophenyl, haloalkyl, alkoxythioalkyl, thiocyano, fursing appropriate starting materials. The compounds furyloxy, alkyldioxolanealkoxy and sulfolaneyloxy. The are listed in Table I.

TABLE I S Example 3 5 .S-l (OCH CH'.-C 'I3)= I i Example 4 Sn-S P (O CH)' i Example 5 SnS P N l ll 2 s Example6 --SnSI OC2H5 Example '7 Example 8 Example 9 Example l0 Example I l Example 1 2 Example I 3 Example l4 Example l5 Example I 6 CH CH INSECTICIDAL EVALUATlON TESTS The following insect species are subjected to evalua- 60 tests for insecticidal activity. 4 Housefly (HF) Musca domestica (Linn) Lygus Bug (LB) Lygus hesperus (Knight) c8 Bean Aphid (BA) Aphis fabae (Scop.) 7

. Two-spotted Mite (Z-SM) Tetranychus um'cae 65 (Koch) 5. Salt-Marsh Caterpillar (SCM) Estigmene acrea tion (Drury) (Hubner) 7. Tobacco budworm (TBW Heliothis virescens (Fabricius) 6. Beet armyworm (BAW) Spodoptera exigua Aliquots of the toxicants, dissolved in an appropriate solvent, are diluted in water containing 0.002% of a wetting agent, Sponto 221 (a polyoxyether of alkylated phenols blended with organic sulfonates). Test concentrations range from 0.1% downward to that at which 50% mortality is obtained. In the tests, for these species, l-month old nymphs of the Lygus Bug are placed in a circular cardboard cage sealed on one end with cellophane and covered by a cloth netting on the other. Test concentrations for the Lygus Bug ranged in this test are found in Table ll under the Columns ZSM-PE and ZSM-Eggs.

The compounds are also active against bean aphid (Aphis fabae (Scop.)) as a contact toxicant. The same from 0.05% downward to that at which 50% mortality 5 test procedure as given for the two-spotted mite above was obtained. Each of the aqueous suspensions of the is used for the bean aphid except nasturt u r p candidate compounds are sprayed onto the insects lum sp.) plants approximately 2 to 3 inches tall are used through the cloth netting by means ofa hand spray gun. as the host plant. The LD values obtained for the Per cent mortality in each case is recorded after 72 compounds of this invention are found in Table I1 hours, and the LB value expressed as per cent of toxide Colum BA- TABLE ll HF LB I BA SMC BAW TBW Example ugl+ t I I I 1 a 0v Z 1 8 0.01 0. 1 1 |0 I cant in the aqueous spray is recorded. The results are in Table ll under Column LB.

The following procedure is used to test houseflies: A stock solution containing 0.l per cent by weight of the toxicant in an appropriate solvent is prepared. Aliquots of this solution are combined with l milliliter of an acetone-peanut oil solution in a glass Petri dish and allowed to dry. The aliquots are selected to achieve desired toxicant concentration ranging from I00 pg per Petri dish to that at which 50% mortality was attained.

The Petri dishes are placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies are introduced into the cage and the per cent mortality is recorded after 48 hours. The LD values are expressed in terms of pg per 25 female flies. LD values obtained in the above-mentioned housefly test are found in Table II under Column HF.

The compound is dissolved in the appropriate solvent and diluted to a concentration of 0.l per cent with water containing 0.015% Sponto 22 l. A portion of the leaf from a bitter dock (Rumex obtuszfolius) plant is immersed in the test solution for 10 seconds and allowed to dry. When dry, the leaf is placed in a Petri dish containing a 9 cm disc of moistened filter paper. Five 3rd- 50 The compounds are also active against two-spotted mite (Z-SM) Tetranychus urticae (Koch). Pinto bean plants (Phaseolus sp.) are utilized as the host plant and infested with 50 to 75 mites of various ages. Twentyfour hours after infestation, they are sprayed to the point of run off with aqueous suspension of the toxi- 65 cant. Test concentrations range from 0.05% to that at which 50% mortality is obtained. The values obtained The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. in these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays;

propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In

connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal composi tions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray.

While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

What is claimed is:

1. A method of killing insects and mites which comprises contacting them with a lethal amount of a compound of the formula CH -CH CH CH CH 3. The method as set forth in claim 1 wherein X is S and R, and R, are

4. The method as set forth in claim 1 wherein X is S and R, and R, are O--CH,CH,Cl-l

5. The method as set forth in claim 1 wherein X is S and R, and R, are -OC,l-l

6. The method as set forth in claim 1 wherein X is S and R, and R are 7. The method as set forth in claim 1 wherein X is S,

10 R, is c,H and R, is 0c.H,.

8. The method as set forth in claim 1 wherein X is S, R, is -C,H and R is cH OCH cn.

9. The method as set forth in claim 1 wherein X is S, R, is CH Cl and R is -OC H 10. The method as set forth in claim 1 wherein X is S, R, is C H and R, is

ll. The method as set forth in claim 1 wherein X is 0 and R, and R are OCH 12. The method as set forth in claim 1 wherein X is S,

R, is C,H,, and R, is SCN.

13. The method as set forth in claim 1 wherein X is S, R, is -C,l'l, and R, is OCH,CH,S(CH ),CH,,.

14. The method as set forth in claim 1 wherein X is O, R, is CH,, and R is -OC H 

1. A METHOD OF KILLING INSECTS AND MITES WHICH COMPRISES CONTACTING THEM WITH A LETHAL AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method as set forth in claim 1 wherein X is S and R1 and R2 are
 3. The method as set forth in claim 1 wherein X is S and R1 and R2 are
 4. The method as set forth in claim 1 wherein X is S and R1 and R2 are -O-CH2-CH2-CH3.
 5. The method as set forth in claim 1 wherein X is S and R1 and R2 are -O-C2H5.
 6. The method as set forth in claim 1 wherein X is S and R1 and R2 are
 7. The method as set forth in claim 1 wherein X is S, R1 is -C2H5 and R2 is -OC2H5.
 8. The method as set forth in claim 1 wherein X is S, R1 is -C2H5 and R2 is
 9. The method as set forth in claim 1 wherein X is S, R1 is -CH2Cl and R2 is -OC2H5.
 10. The method as set forth in claim 1 wherein X is S, R1 is -C2H5 and R2 is
 11. The method as set forth in claim 1 wherein X is O and R1 and R2 are
 12. The method as set forth in claim 1 wherein X is S, R1 is -C2H5 and R2 is SCN.
 13. The method as set forth in claim 1 wherein X is S, R1 is -C2H5 and R2 is -OCH2-CH2-S-(CH2)4-CH3.
 14. The method as set forth in claim 1 wherein X is O, R1 is -CH3 and R2 is -OC2H5. 